Ether-containing mixtures in flexible PVC

ABSTRACT

Heavy organic by-products obtained by hydroformylating olefins and hydrogenating the crude product to obtain higher alcohols, and their steam cracked derivatives, have been found useful as viscosity modifiers and low temperature property improvers in flexible PVC compositions.

This is a division, of application Ser. No. 803,085, filed Nov. 27,1985, now U.S. Pat. No. 4,656,215.

This invention relates to certain ether-containing mixtures derivablefrom the crude products of hydroformylation processes and to the use ofsuch mixtures as components of flexible polyvinyl chloride (PVC)compositions.

The hydroformylation process, in general terms, is a process involvingthe preparation of oxygenated organic compounds by the reaction ofcarbon monoxide and hydrogen (synthesis gas) with carbon compoundscontaining olefinic unsaturation. The reaction is performed underhydroformylation conditions in the presence of a carbonylation catalystor catalyst precursor such as dicobaltoctacarbonyl, and results in theformation of a compound e.g. an aldehyde which has one more carbon atomin its molecular structure than the feedstock. Subsequent hydrogenationof the primary product leads to higher alcohols which may be used forexample for conversion into plasticizers.

Typically in higher alcohol production the feedstock for ahydroformylation process is a commercial C₆ -C₁₂ olefin fraction and thedesired end product is the respective C₇ -C₁₃ saturated alcohol orderived mixed alcohol product, produced by hydrogenation of the aldehydeoxonation product. By virtue of the nature of the feedstock commonlyavailable to industry, and indeed of the catalyst and reactionparameters employed, the oxonation reaction inevitably yields a range ofproducts due to the numerous secondary reactions which take place. Themain commercial products of the hydroformylation reaction are aldehydesand alcohols, with side reactions in the oxonation, demetalling andhydrogenation sections of the process system usually producing some 5 to20 wt. % of high boiling materials. Such high boiling materials, whichrepresent a serious yield loss to the alcohol producer, are formed inlarge part by condensation, esterification and dehydration reactions.

In a conventional higher oxo alcohol process, the feedstock as describedabove is fed together with synthesis gas into an oxonation unit wherecatalytic hydroformylation takes place using e.g.hydrocobalt-octacarbonyl as the active catalyst species. The oxonationunit product passes to a unit for removing catalyst, and then to ahydrogenation unit where it is hydrogenated to form the desired higheralcohol. The product mixture at this stage, comprising the higheralcohol, the high boiling materials mentioned above and a low boilingfraction is then passed to a distillation unit where low boilingmaterials, high boiling materials and desired alcohol product arephysically separated.

The low boiling material passing off overhead is a low value product,typically containing unreacted olefin feed and paraffins. The highboiling material usually contains dimers such as ethers andether-alcohols (e.g. C₂₀ compounds in C₁₀ alcohol production) andtrimers such as acetals (e.g. C₃₀ compounds in C₁₀ alcohol production)and heavier; although substantially alcohol free (apart from the heavyether-alcohols), it may contain a minor amount of alcohol which has notbeen removed in the distillation stage where the higher alcohol majortarget product of the hydroformylation process is separated. Hithertosuch high boiling materials or bottoms products have been conventionallypurged from the system at low value. It is desirable, therefore, todevelop a more profitable use of such materials, and after considerableassessment of the characteristics thereof a surprising new applicationhas been proved.

Some uses have already been proposed, but principally these are directedto uses which involve further treatment of the high boiling materials inorder to improve the economics of the oxo process. An example is theteaching of U.S. Pat. No. 4,048,233 (Ruhrchemie AG), according to whichhigh boiling material (termed "thick oil" residue in that document) isconverted to synthesis gas (H₂ /CO mixture) by catalytic splitting athigh temperatures using defined proportions of water vapour and carbondioxide and a catalyst containing from 2 to 25 wt. % nickel, optionallyon a carrier such as alumina. The splitting takes place at temperaturesof from 600° to 900° C. and pressures up to 30 atmospheres, and thesynthesis gas product is recycled to the oxonation unit. Indeed thedocument teaches that after initial start up the synthesis gas productmay constitute the sole supply of said gas to the system.

According to one of its aspects, the present invention provides for theuse of a hydroformylation-coproduct mixture as a viscosity regulatorand/or low temperature performance improver for flexible polyvinylchloride (PVC) compositions; such a mixture comprises ether,ether-alcohol and acetal components and is the bottoms product obtainedby hydrogenation and subsequent distillation of the crude productderived from the catalytic hydroformylation of a C₆ -C₁₂ olefinicfeedstock with synthesis gas.

The hydroformylation process in which the crude product is formed may beconsidered as entirely conventional and in accordance with the generalhydroformylation process disclosures made hereinbefore. Thus thecatalyst may be for example cobalt based and the operating temperatures,pressures and other conditions such as synthesis gas composition may becontrolled in accordance with the usual expertise of the person skilledin the art to maximise yield of the desired higher alcohol product. Forexample the hydroformylation reaction may be carried out at a pressureof 150-300 atm, and a temperature of from 125°-175° C. The catalyst maybe used in desired active form, for example in a concentration of from0.05-3 wt. % as metal based on the olefinic feed. Typically thesynthesis gas used might have a H₂ :CO volume ratio in the range0.9:1-1.5:1.

The mixtures which have been found useful for the purpose definedhereinbefore are preferably those derived from olefinic feedstockshaving carbon numbers of 8-9. Preferably such mixtures have a specificgravity of from 0.81-0.87, more preferably 0.83-0.85. It is preferredtoo that the mixture has distillation characteristics at atmosphericpressure of initial boiling point (IBP) from 240°-310° C., morepreferably 260°-300° C. and final boiling point (FBP) from 310°-380° C.,more preferably 330°-350° C. Being based on C₆ -C₁₂ feedstock andcontaining up to trimeric components (or even heavier) by virtue of thenature of the reactions and side reactions occuring under the conditionsin the hydroformylation reactor, the mixture used in accordance with theinvention will comprise compounds having carbon numbers in the range7-39.

It is also preferred that the mixtures employed for the specified useare characterised by a flash point of from 140°-170° C. and/or anacidity (mg KOH/g) of from 0.1-3.0, more preferably below 1.0 and/or ahydroxyl number (mg KOH/g) of from 13-160, more preferably below 115and/or a carbonyl number (mg KOH/g) of from 3-30 and/or a pour point ofless than -30° C.

In general coproduct mixtures which have been found to be particularlyuseful for the specified purpose have from 15-25 wt % ether component,from 45-65 wt % ether-alcohol component from 5-25 wt % acetal componentand from 2-10 wt. % of ester component. Depending on the distillationconditions applied following the hydrogenation stage of thehydroformylation process, the bottoms product may contain a minoramount, for example up to 5 wt %, of light alcohol components. Howeverit is preferred that such alcohols be substantially completely removedin order to increase the carbon number range lower limit for alcohols inthe mixture to C₁₄ ; the presence of lower molecular weight alcohols inflexible PVC compositions may lead to an odour and/or exudation problem.Preferably the mixtures used comprise a major proportion of compoundswith carbon numbers in the range 18-24, and they may also contain asmall amount e.g. up to 2 wt. % of extremely heavy compounds.

It has been found that not only is the bottoms product defined anddescribed hereinbefore effective for the specified use in flexible PVCcompositions, but so is the derivative of such bottoms product which isobtained by a further steam cracking treatment thereof. Our copending UKpatent application No. 84 3022 ref PM 81 ECE 004 and entitled"Hydroformylation of Olefins" describes and claims a process primarilyconcerned with the production of higher alcohols from an olefinicfeedstock. Such process comprises hydroformylating the feedstock withsynthesis gas in the presence of a hydroformylation catalyst to form aproduct mixture containing higher aldehyde, alcohol, unreacted feed andsecondary products; removing catalyst therefrom; hydrogenating thesubstantially catalyst free mixture to convert the higher aldehyde tohigher alcohol; distilling the higher alcohol-containing product mixtureto separate (i) a lower boiling Light Oxo Fraction (LOF) and (ii) thedesired higher alcohol from (iii) a higher boiling Heavy Oxo Fraction(HOF); subjecting the HOF to catalytic steam cracking at a temperatureof from 260° to 380° C. using as catalyst an active metal oxide orpseudo-metal oxide, to form HOF residue and a cracked HOF mixturecomprising a major proportion of higher alcohol and higher aldehyde, anda minor proportion of olefin and saturated hydrocarbon; and recyclingthe cracked HOF mixture to the hydroformylation or hydrogenation stageof the process.

In the case where the olefinic feedstock is C₆ -C₁₂, preferably C₈ -C₉,the HOF corresponds to the bottoms product defined hereinbefore, and thecatalytic steam cracking step applied thereto results in the formationof an ether-rich derivative termed in our above mentioned copendingpatent application the HOF residue. This residue has substantially thesame type of components as the described bottoms product mixture, but indifferent proportions and with generally heavier compounds present.Moreover its preferred characteristics of carbon number range, specificgravity, distillation characteristics, flash point, acidity, hydroxylnumber, carbonyl number and pour point correspond with those expressedhereinbefore in relation to the bottoms product. A further aspect of thepresent invention therefore provides an ether-richhydroformylation-coproduct mixture comprising ether, ether-alcohol andacetal components which is obtained by hydrogenation and subsequentdistillation of the crude product derived from the catalytic oxonationof a C₆ -C₁₂ olefinic feedstock with synthesis gas to yield a bottomsproduct, followed by catalytic steam cracking of such bottoms product at260°-380° C. using as catalyst an active metal oxide or pseudo metaloxide.

Yet another aspect provides for the use of such an ether-richhydroformylation-coproduct mixture as a viscosity-regulator and/or lowtemperature performance improver for flexible polyvinyl chloride (PVC)compositions. In a preferred form the ether-rich derivative comprisesfrom 45-75 wt % ether component, from 20-35 wt % ether-alcohol componentand from 1-6 wt % acetal component. Depending on the nature of thefurther process steps employed to separate the mixture from the othermaterials formed or present during the cracking stage (water removal,olefin/saturated hydrocarbon removal, aldehyde/ alcohol removal) themixture may include an alcohol/aldehyde component, for example up to 10wt %. However as with the bottoms product, this is preferably removedbefore use in PVC compositions since alcohol/aldehyde components mayintroduce odour and exudation problems for the proposed use. The derivedether-rich mixtures may, in addition to the components specified above,also contain an ester component for example up to 7 wt. % resulting fromthe various side reactions which occur in the process by which themixtures are produced, and for example up to 1 wt. % of extremely heavycompounds.

The ether rich coproduct mixture is generally heavier than the bottomsproduct, by virtue of the hydrolysis stage and subsequent removal of thealcohol/aldehyde components produced, which are at the lighter end ofthe carbon number range. Thus the ether-rich material is principallydimers, trimers and even heavier derivatives based on the carbon numberof the higher alcohol which is the initial target product of thehydroformylation reaction from which the coproduct mixture is obtained.

This is in comparison with the bottoms product discussed hereinbefore,where principally it is only the lighter alcohols which are preferablyremoved, but other "monomeric" compounds remain in the mixture.

The catalysts which may be employed to promote hydrolysis of thecomponents of the bottoms product, which generally contains alcohol(assuming not all have been removed in the preceding separation stage),ethers, esters, ether-alcohols and acetals, is selected such that thehydrolysis reaction takes place at the rather severe conditions definedto yield a product mixture which in addition to the ether-rich mixtureis relatively enriched in higher alcohols and aldehydes. The catalysedreactions performed under the specified conditions may be for exampleacetal hydrolysis, ester hydrolysis, or ether hydrolysis.

It has been found that the desired reactions take place in the presenceof metal or pseudo-metal oxides in the active state, such as silica,alumina or titanium dioxide, or mixed silica/alumina. It is particularlypreferred to employ alumina as the hydrolysis catalyst.

Such catalysts, under the temperature specified, at least partiallyconvert the bottoms product (HOF) to alcohols and aldehydes, and ofcourse to the ether-rich mixture.

The temperature at which the HOF steam cracking step is performed ismost preferably in the relatively high range of 290° to 360° C., andpreferably at pressures of from 100 to 1000 kPa (1-10 bar), morepreferably 1-3 atm abs. It is preferred that the hydrolysis of the HOFis performed with the weight ratio of steam and HOF in the range 0.1:1to 2:1, more preferably 0.2:1 to 1.2:1. For economic reasons the optimumrange has been found to be from 0.15:1 to 0.5:1.

Following steam cracking of the HOF the ether-rich mixture or HOFresidue, which is typically oxygenated dimers and trimers (C₂₀ -C₃₀ +materials for a C₁₀ alcohol), is separated in a subsequent stage(preferably by a method including steam or flash distillation); howeverthe ether-rich mixture may be automatically separated during the steamcracking step by virtue of the particular cracking technique employed.

The invention defined herein relates to the use of the specifiedmixtures as a component of flexible PVC compositions. Such compositions,in order to have a degree of flexibility, must contain a plasticizer,and it will be appreciated that the scope of the invention extends notonly to the addition of the hydroformylation-coproduct mixtures to thealready plasticized PVC, but also to the simultaneous mixing of themixtures and plasticizer into the PVC, and the admixing of theplasticizer after the oxo-coproduct mixture has been incorporated in thePVC. A further aspect of the invention therefore provides a flexible PVCcomposition which comprises PVC, a plasticizer therefor, andhydroformylation-coproduct mixture (bottoms product or ether-rich) ashereinbefore defined. Such compositions may be in the form of aplastisol, or for example in the form of heat-fluxed compounds such ascalendered or moulded or extruded articles, e.g. extruded cablecovering.

It will be appreciated that the plasticizer used should be compatiblewith the hydroformylation-coproduct mixture, and that the plasticizerand mixture may be added to the PVC as a pre-prepared formulation. It isparticularly preferred that the plasticizer should be a phthalate, morepreferably one produced by esterification of a higher alcohol producedby a hydroformylation process using olefinic feedstock of carbon numberscorresponding to that employed in the production of thehydroformylation-coproduct mixture itself. Preferred plasticizers whichare used in conjunction with the hydroformylation-coproduct mixtures arephthalates of medium range molecular weight such as diisooctylphthalate(DOP), diisononylphthalate (DINP) and diisodecylphthalate (DIDP).

The mixtures, which are believed to function as plasticizers, arepreferably used in amounts corresponding to up to 30 wt % of the totalplasticizer (conventional plasticizer plus hydroformylation-coproductmixture) content of the flexible PVC compositions, more preferably 5-30wt %, and especially 10-20 wt %. Conventionally, flexible PVCcompositions contain for example from 50-75 parts by weight ofplasticizer per 100 parts by weight PVC, together with, optionally,amounts of filler and other conventional additives depending on theintended end use of the PVC compositions.

It is preferred that the mixtures as specified herein for the stateduses, formulations and compositions are subjected to treatment stagesafter or during production in order to reduce their odour and/or colourand/or acidity. Conventional finishing techniques may be used for thispurpose, and the resulting mixtures, being substantially water white,odourless and of low acidity are of particular value in flexible PVC.The mixtures have been found to be particularly useful when employedwith conventional PVC plasticizers to give a desired viscosity reductionof the blends (when in paste form) and/or a useful improvement in lowtemperature performance e.g. flexibility when in moulded, sheet orextruded form.

The invention is illustrated by the following examples, of whichExamples 1 and 3 demonstrate a method of producing a bottoms productform of the oxo-coproduct mixture; Examples 2 and 4 demonstrate thefurther conversion of such mixtures to their ether-rich forms; and theremaining Examples demonstrate the new uses of the mixtures.

EXAMPLE 1

A hydroformylation process for producing higher alcohol was performedusing a feed comprising (i) syn gas containing hydrogen and carbonmonoxide in a molar ratio of 1.16:1 and (ii) a commercially availablestream of branched nonenes including also about 2 wt % octenes and about8 wt % decenes. The olefin feed was delivered at a rate of 1.5 1/hr(1115 g/hr), and the syn gas at a rate of 640 standard 1/hr, into three1.0 liter capacity oxonation reactors arranged in series, and thereaction was carried out at a pressure of 300 atm and a temperature of175° C., using a cobalt catalyst at 0.3 wt % based on the feed. Theresultant crude oxo product containing higher aldehyde was decobalted toless than 10 ppm cobalt in conventional manner by neutralizing thecobalt hydrocarbonyl with sodium hydroxide and washing with water, andthereafter was fed to a conventional hydrogenation train where, usingCu/Cr and Ni catalysts, a hydrogen pressure of 50 bar and a temperatureof 120°-170° C. a product mixture containing the desired higher alcoholwas formed.

This product mixture was then distilled under vacuum to produce threefractions, a light oxo fraction (LOF), a higher alcohol fraction (HA)and a bottoms product or heavy oxo fraction (HOF) as shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Fraction                                                                             Amount      Alcohol content                                                                           Boiling Range                                  ______________________________________                                        LOF    150 g/hr    ≦ 0.5 wt %                                                                         125-187° C.                             HA     1010 g/hr               187-217° C.                             HOF    223 g/hr      ≦3 wt %                                                                            >217° C.                              ______________________________________                                    

The higher alcohol yield (chiefly C₁₀, with minor amounts of C₉ and C₁₁)was 90.58 g per 100 g of feed olefin.

By analysis the HOF, that is the bottoms product or oxo-coproductmixture, was shown to comprise approximately:

    ______________________________________                                         2 wt %     C.sub.9 -C.sub.11 alcohols                                        85 wt %    C.sub.18 -C.sub.22 ethers, ether-alcohols and esters               12 wt %    C.sub.27 -C.sub.33 acetals                                          1 wt %    Heavies                                                            ______________________________________                                    

EXAMPLE 2

The bottoms product mixture (HOF) produced in Example 1 was introducedin upflow manner and in admixture with half its weight of steam into asteam cracking reactor. The reactor was packed with an active aluminacatalyst ALCOA H151 and operated at 318° C., and a pressure of 1.2 atm.The flow of HOF/steam through the reactor was such as to correspond to aspace velocity of 0.5 v/v/hr expressed as volume of HOF per volume ofcatalyst per hour. After cracking, the cracked product was subjected toflashing at 200° C., to produce an overhead stream comprising aso-called cracked HOF mixture and water (steam), and a bottoms stream ofan ether-rich hydroformylation-coproduct mixture (also termed HOFresidue). The HOF residue (54 g/hr) comprised a major proportion ofoxygenated compounds of carbon number C₁₈ -C₃₀ (predominantly C₁₈ -C₂₂)with some even heavier products, and a minor proportion (6.2 wt %) ofalcohol/aldehyde/olefin components. The cracked HOF mixture (169 g/hr)obtained after condensation of the overheads and separation of watercomprised a small proportion of HOF residue, a smaller proportion of anolefin fraction, generally C₈ -C₁₁ olefins with predominantly C₁₀ olefinand a very low level of saturated hydrocarbon, and a major proportion ofan alcohol/aldehyde mixed fraction with carbon numbers C₉ -C₁₁,predominantly C₁₀.

EXAMPLE 3

A hydroformylation process was performed in the same apparatus asExample 1 under conditions of 165° C., 300 atm and using cobalt catalystat 0.15 wt % based on the feed. However, the feed in this case was 1.51/hr (1095 g/hr) of a commercial branched octene feed containing inaddition to C₈ olefin, about 1% of C₇ olefins and about 10% of C₉olefins. The syn gas was employed at a rate of 750 standard liters/hr,and contained hydrogen and carbon monoxide in a ratio of 1.18:1.

Demetalling and hydrogenation of the crude product was performed as inExample 1, with the hydrogenated product being separated by distillationinto the three fractions as shown in Table 2. Thehydroformylation-coproduct mixture (HOF) was the fraction boiling at206° C. and above.

                  TABLE 2                                                         ______________________________________                                        Fraction                                                                             Amount      Alcohol content                                                                           Boiling Ranges                                 ______________________________________                                        LOF    150 g/hr    > 0.5 wt %  113-184° C.                             HA     1013 g/hr               184-206° C.                             HOF    219 g/hr      ≦ 3 wt %                                                                           >206° C.                              ______________________________________                                    

This yield of higher alcohol corresponds to an amount of 92.5 g per 100g of feed olefin.

By analysis the HOF was shown to have the composition:

    ______________________________________                                        1      wt %     C.sub.8 -C.sub.10 alcohols                                    87     wt %    C.sub.16 -C.sub.20 ethers, esters and ether-alcohols           11     wt %    C.sub.24 -C.sub.30 acetals                                     1      %       Heavies                                                        ______________________________________                                    

EXAMPLE 4

The bottoms product hydroformylation-coproduct mixture produced inExample 3 was subjected to catalytic steam cracking in a reactor packedwith ALCOA H 151, at 310° C., a pressure of 1.1 atm and a space velocityof HOF equal to 0.47 v/v/hr. The amount of steam used was 25% of theweight of HOF. Two cracked product streams were obtained following flashat 196° C. and removal of water. The ether-rich mixture (HOF residue)stream (46 g/hr) was the flash liquid phase and was found to compriseC₁₀ -C₂₇ oxygenated compounds, predominantly C₁₆ -C₂₀ materials, with 7wt % other minor components including some aldehyde, alcohol and olefin.The other stream (173 g/hr), being the flash vapour phase, comprised anolefin fraction (10 wt %) which was a mixture of C₇ -C₁₀ olefins,predominantly C₉ 's together with small amounts of saturatedhydrocarbons, and an alcohol/aldehyde fraction (69.2 wt %) containing aC₈ -C₁₀ carbon number range, with a major amount of C₉alcohols/aldehydes.

EXAMPLE 5

Plastisols, that is pastes comprising PVC-Solvic 367 NC (100 parts byweight) and a plasticizer formulation (60 parts by weight) were producedusing a range of formulations by a simple mixing technique. Plastisolsare conventionally used for forming at room temperature into requiredshapes (e.g. of gloves, wall coverings, tarpaulins) followed by heatingto yield generally flexible artefacts. It is important, therefore, thatplastisols should have viscosity characteristics (initial and afterageing) which are suitable for this use. The plastisols produced weresubjected to medium-high shear rate viscosity measurement using a Haakeviscometer. This instrument comprises coaxial cylinders, the inner oneof which is mobile. The material under measurement is contained as afilm between the two cylinders. Measurements were made at a rate of 644sec⁻¹ and at room temperature (23° C.), initially immediately afterproduction of the plastisol and then after ageing for 72 hours. Theresults are shown in Table 3, from which it may be seen that theinclusion of both bottoms product hydroformylation-coproduct mixture andits ether-rich derivative in flexible PVC compositions has a viscositydepressing effect which is maintained even after ageing. The viscositydepressing effect was seen at both high and low shear rates in theviscosity measurement technique which was employed.

                  TABLE 3                                                         ______________________________________                                                      Example Number                                                                5A   5B      5C       5D                                        ______________________________________                                        Plasticizer formulation                                                       (60 phr)                                                                      Phthalate       DOP    DINP    DINP   DINP                                    Coproduct (%)   --     --        10(a)                                                                                10(b)                                 Initial viscosity (poises)                                                                    27     25      22     18                                      72 hour viscosity (poises)                                                                    38     29      23     20                                      ______________________________________                                         (a) = Bottoms product hydroformylationcoproduct mixture produced in           Example 1                                                                     (b) = Etherrich hydroformylationcoproduct mixture produced in Example 2  

EXAMPLE 6

A PVC cable composition was prepared by admixing PVC-Solvic 271 GB (100parts), calcium carbonate filler (80 parts), plasticizer formulation (50parts), tribasic lead sulfate heat stabilizer (4 parts) and dibasic leadstearate lubricant (1 part). Various plasticizer formulations wereemployed, including straight DOP, straight DIDP, a formulation withadded mixture according to the invention, and a conventional formulationof 70% DOP with 30% Cereclor S 52, a known chloroparaffin secondaryplasticizer. The cable composition was moulded into pads which were thensubjected to various tests including volatility (7 days at 100° C.);heat stability (specification VDE 0271 at 200° C.); pad volumeresistivity at 70° C.; and retained elongation after ageing for 7 daysat 100° C. Results are shown in Table 4, from which it may be seen thatthe use of a mixture in accordance with the invention results incompositions having characteristics which are highly acceptable to thecable industry.

                  TABLE 4                                                         ______________________________________                                                      Example Number                                                                6A   6B      6C       6D                                        ______________________________________                                        Plasticizer formulation                                                       Phthalate       DOP    DIDP    70 DOP DIDP                                    Coproduct (%)   --     --      --     10(c)                                   Chlorinated paraffin                                                                          --     --      30     --                                      (Cereclor S 52)                                                               Volatility after 7 days at                                                                    4.5    0.7     4.1    1.8                                     100° C. (mg/cm.sup.2)                                                  Retained elongation after                                                                     0      91      0      98                                      7 days at 100° C. (%)                                                  Heat stability at 200° C. 73                                                           96     30      82                                             (minutes)                                                                     Pad volume resistivity at                                                                     3.1    2.4     6      1.7                                     70° C. (10.sup.11 ohm cm)                                              ______________________________________                                         (c) = the hydroformylationcoproduct mixture produced in Example 1        

EXAMPLE 7

A typical PVC shoe compound was produced by melting a mixture ofPVC-Solvic 264 GA (100 parts) and plasticizer formulation (75-85 phr)and thereafter forming the melt into a moulded sheet form. Variousplasticizer formulations were employed, and the resultant compound wasin each case subjected to tests including volatility (7 days at 100°C.); retained elongation after 7 days at 100° C.; and flexibilitymeasurements (Clash and Berg test, Falling Hammer test). Results areshown in Table 5, from which it may be seen that the use ofhydroformylation coproduct mixtures in accordance with the inventionleads to a highly desirable improvement in the low temperatureflexibility characteristics of the PVC compounds.

In this specification, where reference is made to a particular mixturehaving a particular carbon number range or containing a major proportionof compounds having such particular carbon number range, it is meantthat more than 50% by weight of the mixture comprises compounds in thatcarbon number range. In all such cases it is preferred that suchproportion is greater than 80% by weight, and more preferably greaterthan 90% by weight.

                                      TABLE 5                                     __________________________________________________________________________                 Example Number                                                                7A   7B   7C     7D   7E   7F   7G   7H                          __________________________________________________________________________    Plasticizer (phr)                                                                           75   80     83.5                                                                               83   84   79   75     73.5                     Formulation                                                                   Phthalate    DOP  DINP 70 DOP DINP DINP DINP C.sub.6-10                                                                         C.sub.7-11                  Coproduct (wt %                                                                            --   --   --     10(d)                                                                              15(e)                                                                              --   --   --                          on formulation)                                                               Other plasticizer                                                                          --   --    30    --   --   20 DINA                                                                            --   --                          (wt % on formulation)  CERECLOR                                                                      S 52                                                   Clash-Berg flex T.sub.f                                                                    -43  -42  -42    -49  -53  -46  -53  -49                         (°C.)                                                                  Falling Hammer flex                                                                        -41  -40  -38    -45  -50  -47  -52  -50                         (°C.)                                                                  Volatility after 7                                                                            7.2                                                                                2.2                                                                                5.4    4.0                                                                                4.8                                                                                4.2                                                                                3.1                                                                                2.6                      days at 100° C. (mg/cm.sup. 2)                                         Retained elongation                                                                         71   98   87     88   90   53   94   89                         after 7 days at 100° C. (%)                                            __________________________________________________________________________     (d) = hydroformylationcoproduct of Example                                    (e) = hydroformylationcoproduct of Example                                    C.sub.6-10 = linear phthalate plasticizer of carbon number                    C.sub.7-11 = linear phthalate plasticizer of carbon number 7-11          

We claim:
 1. An ether rich hydroformylation-coproduct mixture comprisingether, ether-alcohol and acetal components which is obtained byhydrogenation and subsequent distillation of the crude product derivedfrom the catalytic hydroformylation of a C₆ -C₁₂ olefinic feedstock withsynthesis gas to yield a bottoms product, followed by catalytic steamcracking of such bottoms product at 260°-380° C. using as catalyst anactive metal oxide or pseudo metal oxide.
 2. A mixture according toclaim 1 wherein said steam cracking catalyst comprises alumina.
 3. Amixture according to claim 1 having physical and chemical propertiesselected from a specific gravity of from 0.81-0.87, distillationcharacteristics at atmospheric pressure of initial boiling point from240°-310° C. and final boiling point from 310°-380° C., and a majorproportion of compounds with carbon numbers in the range 7-39.
 4. Amixture according to claim 1 having physical and chemical propertiesselected from a flash point of from 140°-170° C., an acidity (mg KOH/g)of from 0.1-3.0, an hydroxyl number (mg KOH/g) of from 13-50, a carbonylnumber (mg KOH/g) of from 10-130 and a pour point below -30° C.
 5. Amixture according to claim 1 which comprises from 45-75 wt % ethercomponent, from 20-35 wt % ether-alcohol component, from 1-6 wt % acetalcomponent.
 6. A mixture according to claim 1 which containssubstantially no alcohol and comprises a major proportion of compoundswith carbon numbers in the range 14-39.
 7. A mixture according to claim6 which comprises a major proportion of compounds with carbon numbers inthe range 18-24.